Carbamoyloximino-alkenyl-dithiolanes

ABSTRACT

A new group of 2-carbamoyloximino-4-alkenyl-1,3-dithiolanes is disclosed, which are effective pesticidal compounds particularly for controlling soil pests. The compounds are manufactured by reacting a trans- or cis-1,4-dihalogeno-2-butene with a salt of a dithiocarbamic acid to form a 4-alkenyl-2-imino-1,3-dithiolane which is further reacted with hydroxylamine to give the 4alkenyl-2-oximino-1,3-dithiolane which after reacting with an isocyanate or a carbamic acid chloride yields the desired carbamate.

United States Patent Nikles 1 July 18, 1972 [5 CARBAMOYLOXIMINO-ALKENYL- Primary Examiner-Henry R. Jiles DITHIOLANES Assistant ExaminerCecilia M. Shurko Alto e H Goldsmith, Jose hG.Kol d dM A. [72] Inventor: Erwin Nikles, Liestal, Switzerland z s any p o ny an mo [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Feb. 24, 1970 [57] ABSTRACT PP 13,765 A new group of 2-carbamoyloximino-4-alkenyl-l,3- dithiolanes is disclosed, which are effective pesticidal com- [30] Foreign Application Priority Data pounds particularly for controlling soil pests. The compounds are manufactured by reacting a transor cis-l ,4-dihalogeno-2- Feb. 27, 1969 Switzerland ..2966/69 butene with a salt of a dithiocarbamic acid to form a 4 alke ..260 327 M, 424 277 which is further "acted with Eifi i138! ..Co1d11,00 hydmylmne to w the 4-alkeny1-2mimim-1,s-dimiolane 5a 1 me of Search ..260/327 M which after reacting with an isocyanate or a carhamic acid chloride yields the desired carbamate. [56] References Cited 4 G I No Drawings UNITED STATES PATENTS 3,193,561 7/1965 Addor ..260/327 The present invention relates to l,3-dithiolanyloximinocarbamates of the general formula 1 as well as a process for their manufacture and use as active ingredients in pesticidal preparations.

The present invention provides l,3-dithiolanyloximinocarbamates of the general formula in which R and R each represents a hydrogen atom or a lower alkyl group and R represents a lower alkyl group.

The present invention especially provides the compound of the formula The possible syn(a) or anti([3) isomers of the oximecarbamates are included in the scope of this invention; accordingly, no special reference is made to them hereinafter The present invention also provides a process for preparing the l,3-dithiolanyl-oximinocarbamates of the formula I, which comprises reacting a trans or cis-l,4-dihalogeno-2-butene of the general formula Ha1CH2-CR1 R1-CCHzHal R2 --OH1Ha1 RT- -CHzHal in which l-laI" represents a halogen atom, with a salt of a dithiocarbamic acid of the general formula in which R represents a hydrogen atom or any aliphatic or aromatic radical bound by way of a carbon atom and X represents a cation, to form a cyclic compound of the general formula 1 CH2=C S\ s w (III) further reacting the resulting intermediate product with hydroxylamine to obtain the oximino derivative of the formula 11h CH2=C S S (IV) and reacting the latter with an isocyanate R NCO or R NCO or with an alkylor methylalkyl-carbamic acid halide of the formula hal-CO-N(R (R,), in which hal represents a halogen atom, especially a chlorine atom. R, to R have the meanings defined above.

Preferably R represents a lower alkyl group. The term Hal" refers especially to a chlorine or a bromine atom, preferably a chlorine atom. The cation X may be an alkali metal or an unsubstituted or substituted ammonium group.

The reaction temperatures may be varied within a very wide range. The preferred range is from 20 to l00 C. The reaction may be carried out in the presence of a diluent.

The process of the invention is advantageous in that the starting material is easily obtainable and high yields are obtained in a clear, straightforward reaction.

Since the compounds can also be cyclized in a manner known per se using a 1,2-dihalogeno-3-butene as starting material, a high degree of technical efficiency is possible in that, for example, technical dichlorobutene mixtures obtained by the chlorination of butadiene can be used directly for the cyclization process and the desired compound III is obtained as the sole intermediate product.

The compounds of the formula I have a surprising range of biological activity, as is observed either in the far-reaching control of pests or when used in form of herbicides in areas of cultivated plants where they have a favorable effect on the useful plants.

The present invention also provides a pesticidal preparation comprising, as active ingredient, a compound of the general formula I, together with a carrier and/or further active ingredient.

As carriers there may be used, for example, solvents, diluents, dispersants, emulsifier, wetting agents, adhesives, binders or thickening agents.

The compounds of the formula I also act as molluscicides especially against gastropodes which are schistosome carriers. Furthermore, when applied in very small amounts the new compounds display a good microbicidal activity against bacteria and fungi, especially against phytopathogenic fungi, for example, Erysiphe cichoracearum, Alternaria tenius and solani. In the concentrations required for this use no damage to the plants can be detected.

Furthermore, the compounds of the formula I act against nematodes, for example, Panagrellus redivivus, Meloidogyne sp. and others, and have also a very good insecticidal and acaricidal activity which is distinguished biologically in a distinct manner by chemosterilizing properties.

Thus, for example, these carbamates act strongly against houseflies, aphids, caterpillars and beetles, for example, cornweevil and Colorado beetle. Their contact effect surpasses substantially that of the known active substance Carbaryl" (N-methyl-a-naphthyl-carbamate).

Their activity against Phyllodromia germanica, Periphaneta Americana Blatta orientalis, Acheta domertica and Rhodnius prolixus is especially strong.

The new carbamates are, therefore, very suitable for controlling pests in the hygiene sector and in protecting stored products.

Their activity against Diptera, Coleoptera, Rhynchoti and Lepidoptera makes them an especially suitable type of compound. Soil insects can be controlled in the soil with very small amounts.

It should be specially mentioned that known rice pests, for example, Nephotettix cincticeps, Nilaparvata Iugens, Sogatella fureifera or the rice stem borer Chilo suppressalis, and cotton pests, for example, Prodenia or Anthonomus, can all be effectively controlled.

The toxicity of the compounds of the formula 1 towards warm-blooded beings is to times lower than that of 1,3- dithiolanyl-oximino-N-methylcarbamate. They undergo decomposition in the soil and no residues remain in the cultivated soil for a long time.

The oximinocarbamates of the formula I may be used per se or in combination with suitable additives. The formulation to pesticidal preparations has been described in US. Pat. No. 3,329,702, British Pat. No. 1,047,644 and Swiss Pat. No. 424,359. They can be applied in form of solutions, emulsions, concentrates, dusting agents, wettable powders or by spraying and in many cases in form of granulates which ensures in an advantageous manner that the active substance is released over a prolonged period of time. Such granulates can be prepared by dissolving the active substance in an organic solvent, absorbing this solution by a granulated mineral material, for example, attapulgite or SiO and removing the solvent. Alternatively, they are also obtained when the active substances of the formula I are absorbed in the same manner by granulates based on urea-formaldehyde or polyacrylonitrile.

Depending on the purpose to be served, such preparations may also be applied by distribution (for example, spraying and dusting) over large surfaces with the aid of aircraft.

The various forms of application of such preparations may be suitably adapted to the individual purpose by incorporating with them substances that improve the distribution, the adhesion, the stability towards rain and possibly the penetration, for example, fatty acids, resins, wetting agents, glue, casein or alginates.

The compounds of the formula 1 may be present in the pesticidal preparations of this invention as the only active ingredient or in conjunction with usual insecticides, acaricides, nematocides, bactericides, fungicides, herbicides or fertilizers.

As insecticides there are suitable all the organo-phosphorus compounds used in pest control, carbamic acid derivatives, chlorinated hydrocarbons, nitrophenyl derivatives, and also natural active substances, for example, Sabadilla, Rotenones, pyrethrin and others, may be used as mixing partners.

For controlling representatives of the order Acarina the following known acaricides may be preferentially used in combination with the active substances of the formula 1:

Dinocap, Binapacryl, Z-secondary butyl-4,6-dinitrophenylcyclopropionate, Dinobutone, chlorobenside, fluorobenside,

F enson, Ovex, tetradifon, tetrasul, 4-chlorophenyl-2,4- trichlorophenyl-azosulphide, 2,4-dichlorophenylbenzenesulphonate, N'-(4-chloro-2-methylphenyl)-N,N-

dimethylformamidine, Formetanate, Z-butinyI-para-chlorocarbanilate, cyclopropanecarboxylic acid-2-nitro-4-chloranilide or Dicofol.

The concentration in which the preparations are applied may vary within wide limits depending on the kind of application. In general, it ranges from 0.01 to 20 percent by weight for dilute preparations whereas concentrated ones contain 20 to 98 percent by weight of active substance. Preparations of maximum concentration are used, inter alia, in the so-called ULV (ultra low volume) technique with a minimum content of additives. The ULV technique is carried out with sprayers giving an extremely fine spray, preferably with the aid of aircraft.

By the admixture of synergists the activity of the carbamates of this invention can be further strengthened. For this purpose there may be used, for example, Sesamin, Sesamex, Piperonylcyclonenes, piperonyl-butoxide, piperonal bis[2-( 2-butoxyethoxy)ethyl]acetate, sulphoxides, propylisomes, N-( 2-ethylhexyl)-5-norbomene-2,3-dicarboxamide, octachlorodipropyl ether, 2-nitrophenyl-propargyl ether, 4-chloro-2-nitrophenylpropargyl ether and 2,4,5-trichlorophenyl-propargyl ether.

in the following Examples which illustrate the invention parts are by weight, unless otherwise indicated,

E X A M P L E 1 2-lsopropy1imino-4-vinyll ,3-dithiolan 194 Parts of isopropyl ammonium isopropyl dithiocarbamate are stirred at 30 to 35 C. into a mixture of 165 parts of potassium carbonate, 125 parts of cis-l,4-dichloro-2-butene and 1,500 parts by volume of anhydrous alcohol. The suspension is then refluxed for 14 hours, cooled to room temperature and filtered. The filtrate is evaporated, the residue taken up in parts by volume of benzene+cyclohexane 1:1, again filtered and evaporated. The residue is distilled under a high vacuum. The product boils at 106 to 1 12 C. under 0.025 mm Hg pressure. 2-Oximino-4-vinyl-1,3-dithiolan A solution of 16 parts of hydroxylamine hydrochloride in 30 parts of water is added to a mixture of 38.5 parts of 2- isopropylimino-4-vinyl-1,3-dithiolan and 100 parts by volume of alcohol. The whole is refluxed for 5 hours, then poured over 2,000 parts ofice water and taken up with ether. The ethereal solution is extracted with N-sodium hydroxide solution. The alkaline extract is rendered neutral with concentrated hydrochloric acid while being cooled with ice and extracted with chloroform. The chloroform solution is dried over anhydrous sodium sulphate, filtered and evaporated. The product remains behind in form of an oil. 2-Methylcarbamoyl oximino-4-vinyl-1 ,3-dithiolan 8 Parts of methylisocyanate are dropped at 30 to 40 C. into a solution of 20 parts of 2-oximino-4-vinyl-1,3-dithio1an and 0.1 parts of triethylenediamine in 100 parts by volume of dry toluene. The solution is maintained at 40 C. for 14 hours and then evaporated. The residue is crystallized from aqueous methanol and then from toluene+hexane. The product melts at 114 to 117 C. (compound No. 1). When the combined mother liquors are evaporated, a semi-solid product (compound No. 1a) is obtained which corresponds to the stereoisomer of compound 1.

The following compounds are manufactured in this or a similar manner:

EXAMPLES OF FORMULATIONS 1.5 parts of sodium 1 --benzyl-2-stearyl-benzimida-zole-6,3

-disulphonate 3.5 parts of reaction product of para-tertiary octylphenol and ethylene oxide.

Emulsion concentrate Readily soluble active substances may also be formulated as emulsion concentrates with the following ingredients:

20 parts of active substance 70 parts of xylene parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulphonate are mixed together. 0n dilution with water to the desired concentration a spray emulsion is obtained.

Granulate 7.5 g of an active substance of the formula I are dissolved in 100 cc of acetone and the resulting solution is poured over 92 g of granulated attapulgite (mesh width: 24-28 meshes per inch). The whole is thoroughly mixed and the solvent expelled in a rotary evaporator. The resulting granulate contains 7.5 percent of active ingredient.

EXAMPLEZ A dusting agent prepared as described in Example I, containing 5 percent of active substance No. l and the isomer la obtained from the mother liquor of compound 1, produced the following results in the control of pests affecting stored products:

Pest tested Minimum concentration for a 100 lethal effect within 24 hours exposure (mg of active substance per sq. m.)

Sitophilus granarius 6 6 Fur beetle Larva 200 50 House cricket (Achela domestica) 25 25 E X A M P L E 3 Effect against spider mites Bush bean plants (Phaseolus vulgaris) in the 2-leaf stage were infected with spider mites 12 hours prior to the treatment with the active substance by covering them with infested pieces of leaves from a culture so that after this time had lapsed a mite population was present on all stages of development of the plants. The plants were then sprayed with the emulsified active substance with the aid of a chromatographic atomiser until an even coat of droplets had formed on the surface of the leaves. The results were evaluated 7 days later. The plant portions were inspected under a stereo-microscope and the lethal results were calculated.

The following Table shows the lethal valuesobtained with compound I and isomer la against the species Tetranychus articae Koch of normal sensitivity.

In 800 I00 I00 400 80 I00 I00 EXA MPLE4 Contact effect against Musca domestica (L.) and Ceraritis capitata One bottom half each of Petri dishes was treated with 1 ml of an acetonic solution of one of the substances Nos. 1 and la, which contained 1,000, 100, I0, 5 and 2.5 ppm of the active substance. The solvent was then evaporated and under-cooled houseflies were introduced into the prepared Petri dishes and the lids were put on. Each dish contained 10 test flies. After increasing intervals of time the lethal effect for various concentrations was checked. After 4 hours the following killing effects in percent were recorded:

Compound No.

Concentration M. domestica C. capitata 1000 I00 I00.% I00 I00 I00 l 10 I00 5 50 50 2.5 0 50 I000 I00 100 100 I00 I00 la 10 I00 I00 E X A M P L E 5 Effect against Prodenia litura larvae A leaf of Malva silvestris was immersed in an aqueous solution of the active substance No. l or No. la, then placed in a covered Petri dish and 5 larvae of Malva silvestris in the L stage each were placed on the leaf, while keeping the atmospheric moisture constant with a moistened plug of cottonwool. The result of this contact and stomach-poison test was checked after I and 2 days, after having performed a new infestation after 1 day in each test. The results achieved were as follows:

Compound No. Concentration Killing effect after (ppm) 1 day 2 days 1 800 I00 80 400 I00 80 70 la 800 I00 100 400 I00 100 E X A M P L E 6 A. Effect against Rhipicephalus bursa 5 adult, hungry ticks were counted into a small glass tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion containing 100 ppm of the substance under test. The tube was then closed with a standardized plug of cottonwool and turned over to enable the cottonwool to absorb the emulsion of active substance. Evaluation was carried out after 1 week and 2 weeks.

For .each test two repeats were made. Compound No. I showed after 2 weeks a 100 percent lethal effect, as did Compound No. la.

B. Boophilus microplus (larvae) In the method described under (A) about 10 to 20 larvae were introduced into a small tube and treated with 50 ppm of the substance under test in an aqueous emulsion.

Both Compounds Nos. 1 and la achieved a I00 percent lethal effect after 2 weeks.

EXAMPLE7 Effect against Diptera Lucilia sericata (larvae) A dilution series each was prepared with the emulsifiable Compounds Nos. 1 and la. 2 ml of a concentration were mixed with 2 g of chopped horse flesh in a 10 ml glass vessel, and 20 to 30 freshly hatched larvae were then introduced into each vessel. Evaluation was carried out 24 hours later. A concentration of 24 ppm and 12 ppm respectively produced a 100 percent lethal effect after 24 hours.

EXAMPLE8 Effect against soil insects l Larvae of Diabrolica balteala (banded cucumber beetle), 4 to 7 days old, on one end of a strip of filter paper, l cm wide and 90 cm long, which had been impregnated with a solution of the active substance, were placed in a Petri dish. The other end of the strip carried 10 germinated grains of maize as a feed source. The dishes were covered and kept for 48 hours at room temperature, during which time the larvae attempted to travel over the whole length of the strip of filter paper.

This test was repeated once.

The lethal efiect, achieved with an 0005 percent solution of Compound No. l and Compound No. la respectively was 100 percent.

I claim: 1. A l,3-dithiolanyl-oximinocarbamate of the formula Ilh CII2=C S i R: =NOJJ N\ in which R and R each represents a hydrogen atom or a lower alkyl group, R represents a hydrogen atom or a methyl group and R represents a lower alkyl group.

2. A carbamate according to claim I, wherein R represents a hydrogen atom.

3. The carbamate ofthe formula according to claim 1.

4. A process for the manufacture of a 1,3-dithiolanyl-oximinocarbamate of the formula:

in which R, and R each represents a hydrogen atom or a lower alkyl group, R represents a hydrogen atom or a methyl group and R represents a lower alkyl group, which comprises the step of (l) reacting a transor cis-l,4-dihalogeno-2-butene with a salt of a dithiocarbamic acid of the formula:

in which R represents a hydrogen atom or any aliphatic or aromatic radical bound by way of a carbon atom and X represents a cation, to form a cyclic compound of the formula:

(2) reacting said cyclic compound with hydroxylamine to form an oximino derivative of the formula: 

2. A carbamate according to claim 1, wherein R3 represents a hydrogen atom.
 3. The carbamate of the formula according to claim
 1. 4. A process for the manufacture of a 1,3-dithiolanyl-oximinocarbamate of the formula: 